U.S. patent application number 13/904545 was filed with the patent office on 2013-12-05 for integrated process for deasphalting and desulfurizing whole crude oil.
The applicant listed for this patent is JGC CATALYSTS AND CHEMICALS LTD., SAUDI ARARIAN OIL COMPANY. Invention is credited to Omer Refa KOSEOGLU, Koji Nakano, Masaru Ushio.
Application Number | 20130319910 13/904545 |
Document ID | / |
Family ID | 48670064 |
Filed Date | 2013-12-05 |
United States Patent
Application |
20130319910 |
Kind Code |
A1 |
KOSEOGLU; Omer Refa ; et
al. |
December 5, 2013 |
INTEGRATED PROCESS FOR DEASPHALTING AND DESULFURIZING WHOLE CRUDE
OIL
Abstract
The invention relates to processes for removing impurities, such
as asphalt, from whole crude oil. The invention is accomplished by
first deasphalting a feedstock, followed by processing resulting
DAO and asphalt fractions. The DAO fraction is hydrocracked,
resulting in removal of sulfur and hydrocarbons which boil at
temperatures over 370.degree. C., and gasifying the asphalt
portion.
Inventors: |
KOSEOGLU; Omer Refa;
(Dhahran, SA) ; Ushio; Masaru; (Kawasaki City,
JP) ; Nakano; Koji; (Fukuoka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JGC CATALYSTS AND CHEMICALS LTD.
SAUDI ARARIAN OIL COMPANY |
Kawasaki
DHAHRAN |
|
JP
SA |
|
|
Family ID: |
48670064 |
Appl. No.: |
13/904545 |
Filed: |
May 29, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61655732 |
Jun 5, 2012 |
|
|
|
Current U.S.
Class: |
208/86 |
Current CPC
Class: |
C10G 47/20 20130101;
C10G 67/0463 20130101; C10G 67/049 20130101; Y02P 20/10 20151101;
C10G 2300/201 20130101; C10J 2300/0946 20130101; C10J 3/00
20130101; Y02P 20/125 20151101; Y02P 20/52 20151101 |
Class at
Publication: |
208/86 |
International
Class: |
C10G 67/04 20060101
C10G067/04 |
Claims
1. A method for reducing impurities in a hydrocarbon containing
feedstock, comprising: (i) solvent deasphalting said feedstock to
produce an asphalt fraction and a deasphalted oil (DAO) fraction,
in a first reaction chamber; (ii) processing said DAO fraction and
asphalt fraction in separate, second and third reaction chambers;
(iii) hydrocracking said DAO fraction in said second reaction
chamber to remove sulfur and nitrogen therefrom and to distillate
any hydrocarbons contained in said DAO which have a boiling point
over 370.degree. C.; and (iv) gasifying said asphalt fraction via
combining it with oxygen and steam, in said third reaction chamber,
to produce hydrogen therefrom.
2. The method of claim 1, comprising introducing said hydrogen
produced in said third reaction chamber into said second reaction
chamber.
3. The method of claim 1, wherein said solvent deasphalting
comprises mixing said crude oil with a solvent containing
C.sub.3-C.sub.7 carbon atoms, at a temperature and a pressure below
critical temperature and critical pressure of said solvent.
4. The method of claim 3, wherein said solvent comprises n-butane
and isobutane.
5. The method of claim 1, further comprising contacting said crude
oil with a solid adsorbent.
6. The method of claim 3, comprising mixing said crude oil and
solvent at a temperature and pressure below the critical
temperature and critical pressure of said solvent.
7. The method of claim 3, wherein said crude oil and solvent are
combined at a weight ratio of from 10:1 to 200:1 w/w.
8. The method of claim 1, comprising hydrocracking said DAO at a
pressure of from 100-200 bars, a temperature of from 350.degree. C.
to 500.degree. C., an LHSV of from 0.1 to 4.0 h.sup.-1, and a
hydrogen:DAO ratio of from 500 to 2,500 SLt/Lt.
9. The method of claim 1, comprising hydrocracking said DAO in a
series of multiple chambers.
10. The method of claim 1, wherein said hydrocracking chamber is a
fixed bed, ebullated bed, or slurry bed chamber.
11. The method of claim 1, comprising hydrocracking said DAO in the
presence of a catalyst, which contains from 2-40 wt % active metal,
a pore volume of from 0.33-1.50 cc/gm, a surface area of 250-450
m.sup.2/g, and an average pore diameter of at least 50
Angstroms.
12. The method of claim 11, wherein said active metal is a Group
VI, VII, or VIIIB metal.
13. The method of claim 11, wherein said active metal comprises Co,
Ni, W, or Mo.
14. The method of claim 11, wherein said catalyst is presented on a
support.
15. The method of claim 14, wherein said support comprises alumina,
silica, or a zeolite.
16. The method of claim 15, wherein said support is a zeolite.
17. The method of claim 16, wherein said zeolite has been modified
by treatment with at least one of steam, ammonia, or acid, and
contains at least one transition metal.
18. The method of claim 17, wherein said at least one transition
metal is Zn or Ti.
19. The method of claim 1, comprising gasifying said asphalt
fraction at a temperature of from 900.degree. C. to 1700.degree.
C., and a pressure of from 20 bars to 100 bars.
20. The method of claim 1, further comprising adjusting the amount
of asphalt and at least one of oxygen and steam in said third
reaction chamber to provide a stoichiometric balance therebetween
which results in partial combustion of said asphalt.
21. The method of claim 19, wherein said stoichiometric ratio based
on the oxygen:carbon ratio is from 0.2:1:0 to 10:0.2 by weight.
22. The method of claim 19, comprising introducing asphalt and
steam to said third reaction chamber in a ratio of from 0.1 to 1.0
to 10:0.1 based upon weight of carbon in said crude oil.
Description
RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional
Patent Application No. 61/655,732 filed Jun. 5, 2012, incorporated
by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention relates to an integrated process for treating
whole crude oil to remove asphalt and other impurities therefrom.
To elaborate, the integrated process comprises the steps of
separating asphalt from the whole crude oil, followed by treating
the deasphalted oil via hydrotreatment/hydrocracking with a
catalyst, to remove materials such as sulfur and nitrogen. In
parallel, the recovered, asphalt containing fraction can be
gasified, to produce hydrogen that is then used in the
hydrocracking step.
BACKGROUND AND PRIOR ART
[0003] Conventional processes for treating crude oil involve
distillation, and then various cracking, solvent refining, and
hydroconversion processes, so as to produce a desired group of
products, such as fuels, lubricating oil products, petro-chemicals,
chemical feedstocks, and the like. An exemplary process includes
the distillation of the crude oil in an appropriate atmospheric
distillation column, resulting in gas oil, naphtha, other gases,
and atmospheric residuum. This last portion is fractionated further
in a vacuum distillation column, so as to produce so-called vacuum
gas oil, and vacuum residuum. The vacuum gas oil, in turn, is
usually cracked via fluid catalytic cracking or hydrocracking, to
produce more valuable light transportation fuel products, while the
residuum can be processed further, to yield additional useful
products. The methods involved in these processes can include,
e.g., hydrotreating or fluid catalytic cracking of the residuum,
coking, and solvent deasphalting. Any materials recovered from
crude distillation at fuel boiling points have typically been used,
directly, as fuels.
[0004] To elaborate on the processes described, supra, solvent
deasphalting is a physical, separation process, where feed
components are recovered in their original states, i.e., they do
not undergo chemical reactions. Generally, a paraffinic solvent,
containing 3-8 carbon molecules, is used to separate the components
of the heavy crude oil fractions. It is a flexible process, which
essentially separates atmospheric, and vacuum heavy residues,
typically into two products: (i) asphalt and (ii) deasphalted or
demetallized oil, referred to as "DAO" or "DMO," respectively
hereafter. The choice of solvent is left to the skilled artisan,
and is chosen with desired products, yields, and quantities in
mind, as are other process parameters, such as the operating
temperature, and the solvent/oil ratio. As a general rule, as the
molecular weight of the solvent increases, so does solubility of
the oil into the solvent. For example, either propane or a
propane/isobutane mixture is typically used to manufacture lube oil
bright stock. If, on the other hand, the DAO will be used in
conversion practices, like fluid catalytic cracking, solvents with
higher molecular weights (e.g., butane or pentane, or mixtures
thereof), are used. The products of DAO solvation include those
described supra, as well as lube hydrocracking feed, fuels,
hydrocracker feed, fluid catalytic cracking feed, or fuel oil
blends. The asphalt product may be used as a blending component for
various grades of asphalt, as a fuel oil blending component, or as
a feedstock for heavy oil conversion units (e.g., cokers.)
[0005] Conventional solvent deasphalting methods are carried out
without catalysts or adsorbents. U.S. Pat. No. 7,566,394, the
disclosure of which is incorporated by reference, teaches improved
solvent deasphalting methods which employ solid adsorbents. The
improvement in the methodology leads to separation of nitrogen and
polynuclear aromatics from DAO. The adsorbents are then removed
with the asphalt products, and are either sent to an asphalt pool,
or gasified in a membrane wall gasifier, where solids are
required.
[0006] Hydrocracking processes, as is well known, are used
commercially in many refineries. A typical application of a
hydrocracking process involves processing feedstreams which boil at
370.degree. C. to 520.degree. C. in conventional units, and those
which boil at 520.degree. C. and above, in so-called "residue
units." Simply stated, hydrocracking is a process by which C--C
bonds of large molecules in a feedstream, are broken, to form
smaller molecules, which have higher volatility and economic value.
In addition, hydrocracking processes typically improve the quality
of hydrocarbon feedstock, by increasing the H/C ratio by
hydrogenation of aromatic compounds, and by removing organo-sulfur,
and organic nitrogen compounds.
[0007] Given the significant economic benefits that result from
hydrocracking, it is not surprising that there have been
substantial developments in improving hydrocracking processes, and
the development of more active catalysts.
[0008] In practice, hydrocracking units usually include two
principal zones: a reaction zone and a separation zone. There are
also three standard configurations: single stage, series-flow
"once-through"), with and without recycling, and two stage
processes, with recycling. The choice of reaction zone
configuration depends upon various parameters, such as feedstock
quality, the product specification and processing objectives, and
catalyst selection.
[0009] Single stage, once-through hydrocracking processes are
carried out at operating conditions which are more severe than
typical hydrotreating processes, but which are less severe than
conventional full pressure hydrocracking processes. Mild
hydrocracking is more cost effective than more severe processes
but, generally, it results in production of lesser amounts of
desired middle distillate products, which are of lower quality than
the products of conventional hydrocracking.
[0010] Single or multiple catalyst systems can be used depending
upon, e.g., the feedstock processed and product specifications.
Single stage hydrocracking units are generally the simplest
configuration, designed to maximize middle distillate yield over a
single or dual catalyst system. Dual catalyst systems are used in
stacked-bed configurations or in two different reactors.
[0011] Feedstock is typically refined over one or more
amorphous-based hydrotreating catalysts, either in the first
catalytic zone in a single reactor, or in the first reactor of a
two-reactor system. The effluents of the first stage are then
passed to the second catalyst system which consists of an
amorphous-based catalyst or zeolite catalyst having hydrogenation
and/or hydrocracking functions, either in the bottom of a single
reactor or the second reactor of a two-reactor system.
[0012] In two-stage configurations, which can also be operated in a
"recycle-to-extinction" mode of operation, the feedstock is refined
by passing it over a hydrotreating catalyst bed in the first
reactor. The effluents, together with the second stage effluents,
are passed to a fractionator column to separate the H.sub.2S,
NH.sub.3, light gases (C.sub.1-C.sub.4), naphtha and diesel
products which boil at a temperature range of 36-370.degree. C. The
unconverted bottoms, free of H.sub.2S, NH.sub.3, etc. are sent to
the second stage for complete conversion. The hydrocarbons boiling
above 370.degree. C. are then recycled to the first stage reactor
or the second stage reactor.
[0013] Hydrocracking unit effluents are sent to a distillation
column to fractionate the naphtha, jet fuel/kerosene, diesel, and
unconverted products which boil in the nominal ranges of
36-180.degree. C., 180-240.degree. C., 240-370.degree. C. and above
370.degree. C., respectively. The hydrocracked jet fuel/kerosene
products (i.e., smoke point>25 mm) and diesel products (i.e.,
cetane number>52) are of high quality and well above worldwide
transportation fuel specifications. While hydrocracking unit
effluents generally have low aromaticity, any aromatics that remain
will lower the key indicative properties of smoke point and cetane
numbers for these products.
[0014] One major technical challenge posed in hydrotreating and/or
hydrocracking heavy oil fractions or whole crude is the effect of
small concentrations of contaminants, such as organic nickel or
vanadium containing compounds, as well as poly nuclear aromatic
compounds. These organometallic compounds, and others, reduce the
activity or lifetime of hydrotreating catalysts. The contaminants
and polynuclear aromatics cause reduced process performance, a need
for increased capital, and operating costs of refinery processing
units. The metals in the residual fraction of the crude oil deposit
on the hydroprocessing catalyst pores and results in catalyst
deactivation. These problems are addressed and solved in the
disclosure which follows.
[0015] Conventional, prior art processes in the field of the
invention involve distillation of crude oil, followed by treatment
of the light fractions (naptha and diesel fuel) which remain
following distillation. These light fractions are desulfurized
and/or treated (i.e., "reforming" in the case of naphtha) to
improve their quality, and are then sent to fuel pools for further
use. The vacuum residium, referred to supra, is treated via solvent
deasphalting, so as to secure deasphalted oil and asphalt. Asphalt
is then further treated, by being gasified, or it is sent to the
"asphalt pool."
[0016] Prior art processes show the treatment of fractionates or
distillates of crude oil, rather than treatment of crude oil per
se, as in accordance with the invention. See, e.g.,
PCT/EP2008/005210 where distillates are used to produce asphaltenes
and DAO; U.S. Pat. No. 3,902,991, wherein a vacuum residuum is
solvent extracted followed by hydrocracking and gasification of the
DAO and asphalt; published U.S. Patent Application 2011/0198266,
showing treatment of a vacuum residue; published U.S. Patent
Application 2008/0223754, where residues from a distillation
process are used to manufacture asphaltene and DAO; and EP 683 218,
which also teaches treating residual hydrocarbon products. Also
see, e.g., U.S. Pat. Nos. 8,110,090; 7,347,051; 6,357,526;
6,241,874; 5,958,365; 5,384,297; 4,938,682; 4,039,429; and
2,940,920, as well as Published U.S. Patent Application
2006/0272983; PCT/KR2010/007651, European Patent Application 99
141; and Published Japanese Patent Application 8-231965. All
references discussed herein are incorporated by reference in their
entirety.
[0017] The current invention simplifies and improves the prior art
process, by eliminating the need for distillation, and for treating
the naptha and diesel fractions. Rather, the invention, as will be
seen, simplifies whole crude oil processing by hydrocracking the
whole stream, and eliminating the steps referred to supra.
[0018] How the invention is achieved will be seen in the disclosure
which follows.
BRIEF DESCRIPTION OF THE DRAWING
[0019] FIG. 1 shows a schematic depiction of the process of the
invention, suing a single reactor embodiment.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0020] The invention may be best understood by referring to FIG. 1,
which illustrates the general method of the invention as well as a
system used in its practice.
[0021] Referring to FIG. 1, a feedstream of crude oil "10" is added
to a reaction chamber "11," so as to solvent deasphaltize it,
thereby producing an asphalt fraction "12," and a fraction of
deasphalted oil, or "DAO 13" as referred to supra. The manner in
which this fractionation can be accomplished is described, supra,
i.e., a paraffinic solvent containing one or more carbon atoms
containing from 3-8 carbons, is used. No catalyst or adsorbent is
necessary; however, see U.S. Pat. No. 7,566,394, incorporated by
reference, supra, teaching an improved deasphalting process using a
sorbent. No distillation is used, nor are the light components
separated.
[0022] The "DAO" "13" is transferred to a
hydrocracking/hydrotreating zone "14." It is to be understood that,
while FIG. 1 describes a single reactor, the various methods for
hydrocracking, including "once through, series flow," and
"two-stage" reactions, may all be used. The reactor contains one or
more catalysts which remove heteroatoms, such as sulfur and
nitrogen from the DAO. Such catalysts are well known to the art,
and are not repeated herein. Exemplary of such are catalysts
described in, e.g., PCT/US11/46272 filed Aug. 2, 2011 and
incorporated by reference herein. The cracking reaction takes place
in the presence of hydrogen, which is supplied as explained
infra.
[0023] It will be recalled that in addition to the DAO, solvent
deasphalting of the crude oil produces an asphalt fraction "12."
This asphalt fraction is transferred to a gasification chamber
"15," together with oxygen "16" and steam "17" These components,
i.e., the oxygen and steam, may be supplied in pure form, or via,
e.g., atmospheric air. The asphalt, oxygen and steam are combined,
at temperatures and pressures which result in production of
hydrogen. In the depicted embodiment, this hydrogen "18," is
channeled to the DAO hydrocracking unit "14," to supply the
hydrogen necessary for the hydrocracking process to take place. (It
should be noted that the gasification of asphalt is an optional
step, and may be replaced via, e.g., supplying an independent
source of hydrogen). Various products, e.g., gases 19, and upgraded
crude oil 20, result, and products of gasification 21 are used in
the generation of electricity or for other uses.
[0024] By separating the asphalt component of the crude oil from
the DAO, one eliminates problems such as the failing of catalysts
by metals that are present in the asphalt fraction. Catalyst life
cycles are increased, and the need for shut downs of reactors, and
replacement of materials, are decreased.
[0025] In the process as described herein, the hydrocracking
process takes place at standard hydrocracking conditions, i.e.,
pressures ranging from about 100 to about 200 bars, temperatures
ranging from about 350.degree. C. (to about 450.degree. C., LHSVs
of between 0.1 and 4.0 h.sup.-1, and hydrogen oil ratios of from
about 500 to about 2,500 SLt/Lt.
EXAMPLE
[0026] This example describes an embodiment of the invention in
which gasification of the "SDA" fraction was used to produce
hydrogen, which was then used in the hydrocracking of the DAO
fraction. It will be understood that the H.sub.2 may be supplied
via other means.
[0027] A 1000 kg sample of crude oil was solvent deasphalted, using
art known techniques, with butane solvents and adsorbents, in a
reaction chamber, such as is depicted by "11" in FIG. 1. Prior to
deasphalting, the crude oil was analyzed, and the results of this
analysis are presented in the Table, column 1, which follows.
[0028] Following deasphalting, the asphalt fraction and deasphalted
oil, or "DAO," were also analyzed, and these results are presented
in columns 2 and 3 of the Table.
[0029] The asphalt fraction was gasified by oxygen and steam
combining it into membrane wall reactor or gasification chamber,
depicted at "14" in FIG. 1. The mixture was heated to 1045.degree.
C., with a water to carbon ration of 0.6 (in terms of weight), and
an oxygen:pitch ratio of 1.0.
[0030] After gasification was completed, the raw syngas product was
combined with steam that was produced by either a boiler or process
heat exchanger to a water gas shift ("WGS") reactor, which was
operated at 318.degree. C., one bar of pressure, and a water to
hydrogen ratio of 3. This increased hydrogen yield.
[0031] All analyses and results are presented in the table which
follows and which is elaborated upon infra:
TABLE-US-00001 TABLE Summaries of Components Column # 1 2 3 4 5 6 7
8 Stream# 10 13 12 19 20 16 17 18 Stream Arab Deasphalted Asphalt
C1-C4 Upgraded Oxygen Steam Hydrogen Name Heavy CO Crude Oil Crude
Oil Feedrate kg 1000 922 78 4.8 930 78 46.8 13 Density Kg/Lt 0.8904
0.876 1.210 0.825 API Gravity .degree. 27.4 30.0 -14.6 40.1 Carbon
W % 84.8233 85.04 78.36 Hydrogen W % 12.18 12.83 6.43 Sulfur W %
2.837 1.99 10.79 <20 Nitrogen ppmw 1670 535 9575 <20 MCR W %
8.2 2.55 61.3 Nickel ppmw 16.4 1 582 <1 Vanadium ppmw 56.4 1 172
<1 C5- W % 7.8 Asphaltenes C7- W % 4.2 Asphaltenes Toluene W %
0.0008 insolubles Ashes W % 0.014 H2 W % 99.5 H2S W % 2.47 NH3 W %
0.11 C1-C4 W % 100 36-190 W % 17.4 20.6 21.5 190-370 W % 25.8 29.0
36.0 370-490 W % 17.9 19.1 21.2 490+- W % 39.0 31.3 21.2
[0032] While gasification was taking place, the DAO portion was
introduced to a standard, hydrocracking unit, shown in "14," and
hydrocracked at 360.degree. C., 115 bars of hydrogen partial
pressure, with an overall liquid hourly space velocity of 0.3
h.sup.-1, with a Ni--Mo promoted, amorphous VGO hydrocracking
catalyst and a VGO zeolite catalyst, at a loading ratio of 3:1. See
PCT/US11/46272, incorporated supra, for the catalyst used
herein.
[0033] The products which left the hydrocracking chamber were
analyzed for content of low molecular weight hydrocarbons
(C.sub.1-C.sub.4), upgraded crude oil, oxygen, steam, and hydrogen.
These values are presented in columns 4-5 in the Table. The
upgraded crude oil was also analyzed for various minor components,
as well as boiling fractions, in the same way the crude oil, and
DAO were analyzed. To elaborate upon the Table, Column 1 presents
the analysis of the crude oil ("CO") used in the reaction. Column 2
is the analysis of the resulting DAO and Column 3, the asphalt
fraction. Column 4 presents the information on the gas produced in
the hydrocracking step, with Column 5, the upgraded crude oil.
Finally, Columns 6, 7, and 8 refer to the reactants added to the
reactors, as discussed supra.
[0034] The foregoing disclosure sets forth the features of the
invention, which is a simplified methodology for reducing
impurities, such as sulfur and nitrogen, in a feedstock, such as
crude oil, which does not involve distillation. To summarize, the
crude oil is solvent deasphalted, resulting in DAO and asphalt. The
DAO is then hydrocracked in the presence of a catalyst so as to
desulfurize and denitrogenize it, and to convert any hydrocarbons
which have a boiling point over 370.degree. C. into distillates.
Concurrently, the asphalt fraction is gasified so as to produce
hydrogen. In one embodiment, the hydrogen is channeled back into
the hydrocracking reactor and used in that process. The nature of
the feedstock will, of course vary and may include ash in an amount
ranging from about 2% to about 10% of the total feedstock. The
feedstock may be liquid or solid. Liquid feedstocks having
components with boiling points of from about 36.degree. C. to about
2000.degree. C. are preferred. The feedstock may be, e.g.,
bituminous, oil, sand, shale oil, coal, or a bio liquid, and
preferably contains less than 20 ppmw of sulfur.
[0035] In practice, it is desirable to subject the crude oil to a
paraffinic solvent to separate DAO and asphalt. The solvent
comprises one or more C.sub.3-C.sub.7alkanes, which may be straight
chained or branched. Preferably, the solvent comprises one or, most
preferably, a mixture of butanes. Solvation takes place at
temperatures and pressures, which are below the critical values for
both of these.
[0036] It is especially preferred to carry out the deasphalting
step, discussed, in the presence of a solid adsorbent, preferably
added in an amount sufficient to provide a hydrocarbon:adsorbent
ratio of from 20:0.1 to 10:1, expressed in terms of W/W.
[0037] After separation, the DAO is transmitted to a hydrocracking
unit, where hydrocracking is carried out at conditions which may
vary, but are preferably a pressure of from about 100 to about 200
bars, a temperature of from about 350.degree. C. to about
500.degree. C., an LHSV of from about 0.1 to about 4.0 h.sup.-1,
and a hydrogen:oil ratio of from about 500 to about 2500 SLt/Lt.
Any standard hydrocracking system may be used including single
reactors, multiple reactors operated in series, fixed bed reactors,
ebullated bed reactors, and so forth.
[0038] A catalyst is used in the hydrocracking process, preferably
the catalyst incorporated by reference supra. Preferably, the
catalyst contains from about 2% to about 40% by weight of active
metal, a total pore volume of from about 0.3 to about 1.5 cc/g, a
total surface area of from about 200 to about 450 m.sup.2/g, and an
average pore diameter of at least 50 angstroms.
[0039] With respect to the active metal, referred to supra, metals
from Group VI, VII or VIIIB are preferred, and may include one or
more of Co, Ni, W, and Mo. While it is not required to do so, the
catalysts are generally incorporated on a support, such as alumina,
silica, a zeolite or a zeolite modified by, e.g., steam, ammonia,
acid washing and/or insertion of transition metals into its
structure.
[0040] Concurrent with the hydrocracking of the DAO, the asphalt
portion of the crude oil is gasified in a gasification chamber,
e.g., a membrane wall type reactor, preferably at a temperature of
from about 900.degree. C. to about 1700.degree. C., and a pressure
of from about 20 bars to about 100 bars. Gasification takes place
in the presence of an O.sub.2 containing gas, which may be, e.g.,
pure O.sub.2 or more preferably, atmospheric gas. Means may be
provided to control the amounts of asphalt and oxygen entering the
gasification reactor. Such means are well known to the skilled
artisan and need not reiterated here. It is preferred t control the
amounts of asphalt and O.sub.2, so that a stoichiometric balance
permitting partial combustion ensues. This can be determined via
determining the hydrocarbon content of the crude oil, such as was
done in the example, supra. Preferably, the amounts are selected
such that the oxygen:carbon ratio ranges from about 0.2:1.0 to
about 5:0.1 by weight.
[0041] Optionally, steam may be added to the gasification chamber.
When it is, it too is added in an amount based upon the carbon
content of the crude oil, and is preferably presented at a ratio of
from about 0.1:1.0 to about 100:1.0 by weight. Gasification results
in a product sometimes referred to as "syngas" consisting
essentially of hydrogen and carbon monoxide. In one embodiment of
the invention, the syngas produced by gasification is transmitted
to a water gas shift reaction chamber and treated to produce
H.sub.2 and CO.sub.2, after which H.sub.2 is separated. The
resulting, pure H.sub.2 may be channeled to the hydrocracking
reaction.
[0042] The process by which the syngas is treated may include
treatment at a temperature of from about 150.degree. C. to about
400.degree. C., and a pressure of from about 1 to about 60
bars.
[0043] As was seen, supra, gas content can be measured at any point
in the process described here. Hence, following measurement of CO
content in the syngas, water can be added to the reaction chamber,
preferably at a molar ratio with CO of from about 3:1 to about
5:1.
[0044] Other facts of the invention will be clear to the skilled
artisan and need not be reiterated here.
[0045] The terms and expression which have been employed are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expression of excluding any
equivalents of the features shown and described or portions
thereof, it being recognized that various modifications are
possible within the scope of the invention.
* * * * *